Production of polyvinyl alcohol having improved dyeability and composition therefor including polyvinyl alcohol basic nitrogen-containing derivatives



United States Patent "ice corporated, New York, N.Y., a corporation of New York No Drawing. Filed Mar. 18, 1960, Ser. No. 15,300 Claims priority, application Japan, Mar. 20, 1959, 34/ 8,627 6 Claims. (Cl. 260-296) This invention relates to a process of producing fibers of polyvinyl alcohol and polyvinyl alcohol derivatives and is more particularly concerned with a process of forming such fibers which are characterized by desirable properties.

As described in U.S. patent application Ser. No. 856,334, filed December 1, 1959, the dyeability of polyvinyl alcohol fibers can be markedly increased by spinning the fibers from a mixture of an emulsified polymer formed from basic monomers and a water solution of polyvinyl alcohol. When fibers spun from such a mixture are subjected to benzalization, which has the effect of significantly improving the elasticity of polyvinyl alcohol, fibers can be obtained which have excellent elastic recovery and dyeability without showing any significant drop in dyeabsorption. This is substantially different from the results obtained by mixed spinning of water-soluble polymers containing basic nitrogen as heretofore practiced.

It is thus an object of this invention to provide a process for producing fibers of polyvinyl alcohol and polyvinyl alcohol derivatives having high heat-resistance and desirable mechanical properties at least equal to fibers produced solely from polyvinyl alcohol, yet characterized by a particularly high dyeability.

In accordance with this invention, spinning of fibers is effected from a spinning fluid prepared by dispersing in a water solution of polyvinyl alcohol an emulsion or fine powder of a water-insoluble polyvinyl alcohol derivative which has been acetalized by means of aldehydes containing basic nitrogen. In carrying out the process of the invention, the polyvinyl alcohol or derivative may be acetal-ized by means of aldehydes having no basic nitrogen simultaneously with, before or after the treatment with aldehydes containing basic nitrogen.

We have studied extensively the methods of manufacturing of emulsions or fine powders of water-insoluble polymers containing basic nitrogen and we have discovered that by producing emulsions or fine powders of waterinsoluble polyvinyl alcohol and its derivatives subjected to acetalization by means of aldehydes containing basic nitrogen, and with acetalization by aldehydes having no basic nitrogen simultaneously with, or before or after the first-mentioned acetalization step, fibers of the abovementioned desirable characteristics could easily be obtained by spinning a spinning fluid prepared by dispersing such an emulsion or fine powder in a water solution of polyvinyl alcohol. We found particularly that a significant elevation in the dyeability of fiber could be achieved.

As described in said application Ser. No. 856,334, the size of solid particles contained in a stable spinning fluid which is entrely trouble free for the spinning operation, i.e. the size of the so-called emulsified polymer contained in the spun fiber, is usually a few a. In accordance with the present invention, it is possible, with no difficulty, to obtain solid particles having particle diameters of 1,u30 ,L. In this case, larger particles show a smaller drop in dye- 3,211,635 Patented Oct. 12, 1965 ability when subjected tobenzaliza-tion. The reason for this behavior is not entirely understood, but when the surface of fiber is observed by means of the electron microscope, there are observed large cracks along the solid particles of fine powder. Based on these observations, it is believed that in the case of such solid particles, the larger the particle diameter, the less it will be influenced by the structure of the polyvinyl alcohol or acetal, and as a result, the fiber allows dye-stufiFs to permeate with ease. In any event, in view of the present-day demands for fibers derived from polyvinyl alcohol which have high elasticity and dyeability, the industrial significance of the invention is substantial inasmuch as the invention makes it practicable to achieve fibers having these characteristics on an economical basis without accompanying difliculty.

When the particle diameter is large, the percentage of broken yarns and fluffy yarns increases, resulting in a yarn of poorer mechanical properties. Thus it is important for the particle diameter to be 30,41. or smaller. The amount of basic nitrogen in the polymer produced in accordance with this invention is over 0.2%, and the mixing ratio of the polymer to polyvinyl alcohol is adequate if it produces a mixture of ODS-2% content of basic nitrogen. With such a mixture there is achieved a marked increase in dyeability with respect to direct cotton dyes and acid dyes for W001, and any drop in heat-resistance, and hot water-resistance, and mechanical properties is insignificant.

In carrying out the acetalization reaction with a view to obtaining emulsions or fine powders of polymers suitable for the object of this invention, it is generally preferable to effect high-speed stirring, or to add any of various known surface active agents or water-soluble polymers to the reaction fluid.

To form a stable dispersion of the above-described solid polymer particles in a water solution of polyvinyl alcohol, various procedures may be employed. Thus when the polymer is in the form of an emulsion, the emulsion may be directly mixed with a water solution of polyvinyl alcohol, or it may be mixed with polyvinyl alcohol powder and water may then be added to dissolve the powder. Alternatively, the emulsion may be heated, and polyvinyl alcohol powder or moist polyvinyl alcohol powder may be slowly added and dissolved in the emulsion. When the polymer particles are in the form of a fine powder, the powder particles may be mixed with polyvinyl alcohol powder and water added to dissolve the powder mixture or the polymer particles may be mixed with a small amount of water or a water solution of polyvinyl alcohol, and the paste of fine powder thus obtained may be mixed with polyvinyl alcohol. It will be understood, however, that various other procedures may be used. As mentioned, various surface active agents, partially-aminoacetalized polyvinyl alcohol, soluble starch, polyvinylpyrrolidone, and various other types of polymers may be added as protective colloids.

The fiber spun by the method of this invention may be subjected to thermal elongation, heat-treatment and insolubilization treatments in the same manner as fibers formed solely from ordinary polyvinyl alcohol. For effecting insolubilization treatments there may be employed acetalization by means of aldehydes such as form-aldehyde, acetaldehyde, chloracetaldehlyde, butyraldehyde, nonylaldehyde, benzaldehyde, monochlorobenzaldehyde, l-naphthaldehyde, glyoxal, malonialdehyde, glutaraldehyde, terephthaldehyde, and the like.

The fibers may also be subjected to treatments with inorganic reagents such as titanation, and chroming. Various other known insolubilization treatments may also be employed.

It is also practicable to carry out spinning process by adding various types of water-soluble polymers such as soluble starch, polyvinylpyrrolidone, aminoacetalized polyvinyl alcohol, various types of pigments such as titanium oxide, and acids, alkalis, and salts such as sodium sulfate. Accordingly, it is possible to effect simultaneous improvement in transparency and in the shape of the cross-section of the fiber, particularly when the fibers are formed by wet-spinning.

The aldehydes having basic nitrogen which are suitably used in the process of this invention include aliphatic, aromatic, aralkyl, and heterocyclic aldehydes having primary, secondary or tertiary amino groups, such as aminoacetaldehyde, methylaminoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, ,B-aminopropionaldehyde, ,B-methylaminopropionaldehyde, [i-ethylaminopropionaldehyde, fi cyclohexylaminopropionaldehyde, {3 dodecylaminopropionaldehyde, ,8 aminobutyraldehyde, ,B-methylaminobutyraldehyde, fi-ethylaminobutyraldehyde, B-butylaminobutyraldahyde, fi-cyclohexylaminobutyraldahyde, B-nonylaminobutyraldehyde, fl-(Z- ethylhexyl)-aminobutyraldehyde, 19 dodecylaminobutyraldehyde, B-octadecylaminobutyraldehyde, fi-dimethylaminobutyraldehyde, ,8-diethylaminobutyraldehyde, ,EI-dibutylaminobutyraldehyde, B methyl-fi-cyclohexylaminobutyraldehyde, ,B-dinonylaminobutyraldehyde, fi-dimethylaminopivaldehyde, [3-diethylaminopivaldehyde, B-dibutylaminopivaldehyde, B-dinonylaminopivaldehyde, ,B-cyclohexylaminopivaldehyde, fi-nonylaminopivaldehyde, fi-dodecylaminopivaldehyde, fi-octadecylaminopivaldehyde, w, 6-, or 'y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylaminobenzaldehyde, or their acetals, or aldehydes containing nitrogen which have been quaternized by the action of alkylating agents such as methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl p toluenesulfonate, ethyleneoxide, and the like, or their acetals.

As aldehydes having no basic nitrogen, there are suitably used various aliphatic or aromatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexylaldehyde, nonylaldehyde, dodecylaldehyde, chloracetaldehyde, fl-cyanopropionaldehyde, methylglyoxal, malonaldehyde, benzaldehyde, naphthaldehyde, mor p-chlorobenzaldehyde, o-, mor pcyanobenzaldehyde, m-nitrobenzaldehyde, terephthaldehyde, salicylaldehyde, anisaldehyde, tetrahydrobenzaldehyde, trimethyltetrahydrobenzaldehyde, hexahydrobenzaldehyde, phenylacetaldehyde, cinnamaldehyde, and the like, or their acetals.

The invention will be further understood from the following specific examples of practical application. However, it will be understood that these exampes are not to be construed as limiting the scope of the present invention in any manner. In these examples, all parts are by weight.

Example 1 A water solution containing polyvinyl alcohol having a degree of polymerization of 1500, 5% formaldehdye and 20% sulfuric acid was heated from an initial temperature of 30 C. while stirring at the rate of 1000 r.p.m. and was held at 50 C. for 3 hours. The pure white, fine powder of partially formalized polyvinyl alcohol thus obtained was filtered and washed with water. This fine powder was then dispersed by stirring into a water solution containing B-cyclohexylaminobutyraldehyde dimethylacetal (300 mol percent based on the polyvinyl alcohol), and 15% sulfuric acid and the mixture was stirred for 2 hours at 50 C. to eifect aminoacetalization. The amount of basic nitrogen in the fine powder thus obtained was 1.1%.

1 part of this fine powder was mixed with parts of polyvinyl alcohol powder, then dissolved by adding water, and wet-spinning was effected in a sodium sulfate coagulating bath, followed by heat-treatment under a constant yarn length at 235 C. for 30 sec. Formalization was then effected by maintaining a water solution containing a first batch of the spun fibers, 5% formaldehyde, sulfuric acid and 15% sodium sulfate at 70 C. for 2 hours.

A second batch of the spun fibers was subjected to benzalization in a water solution containing the fibers, 3% benzaldehyde, 10% sulfuric acid, and 40% methanol which was maintained at 70 C. for 1 hour. The degree of acetalization was 41.1% for the first fiber batch and 29.5% for the second fiber batch. All of the thustreated fibers were then dyed by means of 2% of acid brilliant scarlet 3R (Colour Index No. 16255) and 10% acetic acid, based on the weight of bier, at 90 C. for 1 hour, during which time both batches absorbed the dyestuff completely. These fibers were compared with a portion of the heat-treated fibers which were not subjected to formalization but were directly dyed, and no drop in dyeability was observed. When compared with ordinary formalized polyvinyl alcohol, however, the fibers of the first and second batches were found much superior in dyeability, and the second batch, viz. the benzalized fiber, had a particularly high elasticity. When the cross-section and the profile of the dyed fiber from the second batch was examined under the microscope, the presence of fine powder was observed.

Example 2 A water solution containing 5% of the partially saponified product of polyvinyl acetate having 15% acetate radicals, 5% formaldehyde, and 15% sulfuric acid was gradually heated from C. with stirring. After 10 minutes, fl-aminopropionaldehydedimethylacetal (200 mol percent based on the polyvinyl alcohol) was slowly added, and the mixture was maintained at 50 C. for 3 hours.

1 part of the fine powder of acetalized polyvinyl alcohol thus obtained in which basic nitrogen had been introduced, was mixed with 10 parts of polyvinyl alcohol, thereby to form a spinning fluid with a total polymer concentration of This solution was subjected to dry spinning by forcing it out into the air through a nozzle having a diameter of 0.3 mm. The fiber was stretched 550%, in a continuous process at 220 C., and was allowed to shrink 20% at 225 C. Then the fiber was benzalized as described in Example 1.

The 28% benzalized polyvinyl alcohol thus obtained was dyed at 95 C. with 4% of acid brilliant scarlet 3R, based on the weight of the fiber. The fiber had an elasticity much superior to that of ordinary formalized polyvinyl alcohol. Similar results were obtained by dyeing with 2% of Nippon fast violet BB.

Example 3 A water solution containing 3% of polyvinyl alcohol having a degree of polymerization of 1000, 1% of formaldehyde and 50% of sulfuric acid (50%) Was maintained at 50 C. for 2 hours while stirring at the rate of 1000 r.p.m. The temperature was then reduced to C., and a water solution containing 1% of a dispersing agent was gradually added to the reaction mixture in a volume radio of 2:1 while stirring at the rate of 1000 r.p.m. There was produced a suspension of polyvinyl formal of a pure white color in finely-divided form. Then the reaction temperature was raised to 70 C., and p-cyclohexylaminobutyraldehydedimethylacetal was added very slowly in the amount of mol percent of the polyvinyl alcohol. The basic radical was then introduced into the polyvinyl alcohol by maintaining the mixture at C. for one hour. The product thus obtained was of a particle size of 510;t, the amount of basic nitrogen introduced being 1%.

The thus-produced emulsion was then dialyzed at 50 C. for 20 hours, and then the formaldehyde, aminoaldehyde and sulfuric acid which had not reacted were removed. Thus an emulsion of insoluble polyvinyl acetal combined with basic nitrogen was obtained.

1 part of this fine particle emulsion was mixed with parts of polyvinyl alcohol and the mixture was spun, heat-treated, and acetalized in the manner described in Example 1. The fiber thus obtained was found to have excellent dyeability, and even when its elasticity was elevated by benzalization, no drop was noted in its dyeability.

The fiber produced in this example was compared with respect to physical properties with fibers produced under the same conditions except for the introduction of basic nitrogen, with the following results:

Results similar to those mentioned above were obtained with fibers produced by dry-spinning of a fine powder or emulsion of insoluble polyvinyl acetal combined with basic nitrogen.

Example 4 A water solution containing 3% of polyvinyl alcohol of a degree of polymerization of 1500, 2% of formaldehyde and 50% of H 50 was maintained at 50 C. for 2 hours while stirring at the rate of 1000 r.p.-m., and then a water solution containing 1% of a dispersing agent was added very slowly at 40 C. in a volume ratio of 2:1 while stirring at the rate of 1000 1.p.m.

Upon completion of this addition finely-divided polyvinyl formal of pure white color was produced. This fine powder was separated by filtering and thorough washing with water. Then the fine powder was reacted in a 5% Water solution containing fl-cyclohexylaminobutyraldehydedimethylacetal (1000 moi percent based on the polyvinyl alcohol), and 20% of H 80 at 70 C. for 1 hour. When the reaction was complete, there was obtained a perfectly semi-transparent emulsion having a basic nitrogen content of 2%. The emulsion was dialyzed, and there was obtained an emulsion containing 5% of formalized fine particles of insoluble polyvinyl alcohol containing basic nitrogen.

1 part of this emulsion was mixed with 20 parts of polyvinyl alcohol and, using the procedure described in Example 1, the mixture was spun, heat-treated and acetalized.

The fiber thus obtained exhibited excellent physical properties similar to those of the fiber obtained in Example 3, indicating the same degree of dyeability even after heat-treatment.

Example 5 By vigorously stirring a water solution of 6% of polyvinyl alcohol, 5% of hydrochloric acid, 5.5% of dodecylaminopivaldehyde and 2% of dodecyltrimethylammonium chloride at 60 C. for 3 hours, an emulsion of amin-oacetalized polyvinyl alcohol was obtained. A portion of this emulsion was dissolved with methanol and then re-precipitated in acetone to purify it. The nitrogen content was found to be 1.44%. A water solution of polyvinyl alcohol was mixed with the emulsion so that the ratio of acetalized polyvinyl alcohol to polyvinyl alcohol was 20:80, and then the mixture was adjusted to be a total polymer concentration of The excess hydrochloric acid was neutralized by an addition of a water solution of caustic soda, and the pH was adjusted to 6.0. The fiber produced from a spinning fluid adjusted to a total polymer concentration of 13% and wet-spun, heat-treated, and formalized in accordance with the procedure described in Example 1 was found to have excellent dyeability both with acid dyes and direct dyes. Similar results were obtained when the fiber was benzalized instead of being formalized.

It will be understood that, unless otherwise indicated, conventional dry-spinning or wet-spinning operations are employed in producing the fibers and subsequent heat treatment, stretching and relaxation are effected in accordance with known techniques. Similarly, conventional apparatus is employed in carrying out the process of this invention including conventional mixing and emulsifying unit-s, spinning devices and fiber treating apparatus. The conditions and the relative relationships set forth in the examples are those preferred in carrying out the proc ess of the invention but it will be understood that other conditions and relationships may be used within the scope of the invention. Similarly, conventional dyeing techniques and apparatus are suitably employed upon the fibers produced by the process of this invention.

It will also be understood that various changes and modifications may be made without departing from the scope of the invention as defined in the appended claims and it is intended, therefore, that all matter contained in the foregoing description shall be interpreted as illustrative only and not as limitative of the invention.

We claim:

1. In the manufacture of polyvinyl alcohol fibers of improved dyeability, the steps which comprise preparing an aqueous spinning fluid comprising a mixture of an aqueous solution of polyvinyl alcohol and a waterinsoluble acetalized polyvinyl alcohol in finely-divided form having a particle size of at most 3051., said acetalized polyvinyl alcohol being acetalized with at least one aldehyde containing basic nitrogen and at least one aldehyde free from basic nitrogen, whereby said acetalized polyvinyl alcohol contains basic nitrogen, and spinning said fluid to form fibers therefrom, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methylaminoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, ,B-aminopropionaldehyde, fiamethylaminopropionaldehyde, ,B-ethylaminopropionaldehyde, B cyclohexylaminopropionaldehyde, li-dodecylaminopropionaldehyde, p-aminobutyraldehyde, B-methylaminobutyraldehyde, B-ethylaminobutyraldehyde, fi-butylaminobutyraldehyde, fi-cyclohexylaminobutyraldehyde, ,B-nonylamino-butyraldehyde, ,8-(2- ethylhexyl)-aminobutyraldehyde, ,8 dodecylaminobutyraldehyde, fi-octadecylaminobutyraldehyde, ,B-dimethylaminobutyraldehyde, fi-diethylaminobutyraldehyde, B-dibutylaminobutyraldehyde, e methyl-fl-cyclohexylaminobutyraldehyde, p-dinonylaminobutyraldehyde, [3-dimethylaminopivaldehyde, fi-diethylaminopivaldehyde, ,B-dibutylaminopivaldehyde, B-dinonylaminopivaldehyde, fl-cyclohexylaminopivaldehyde, fl-nonylaminopivaldehyde, ,B-dodecylarninopivaldehyde, B octadecylaminopivaldehyde, w, ,B-, and 'y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylarninobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof producedby the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-p-toluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

2. In the manufacture of polyvinyl alcohol fibers of improved dyeability, the steps which comprise preparing an aqueous spinning fluid comprising a mixture of an aqueous solution of polyvinyl alcohol and a waterinsoluble acetalized polyvinyl alcohol in finely-divided forrn having a particle size of at most 3011., said acetalized polyvinyl alcohol being acetalized with at least one aldehyde containing basic nitrogen and at least one aldehyde free from basic nitrogen, said polyvinyl alcohol being acetalized with said last-named aldehyde prior to being acetalized with said first-named aldehyde, whereby said acetalized polyvinyl alcohol contains basic nitrogen, and spinning said fluid to form fibers therefrom, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methylaminoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, fl-aminopropionaldehyde, p-methylaminopropionaldehyde, li-ethylaminopropionaldehyde, B-cyclohexylaminopropionaldehyde, fi-dodecylaminopropionaldehyde, fl-aminobutyraldehyde, B-methylaminobutyraldehyde, ,B-ethylaminobutyraldehyde, fl-butylaminobutyraldehyde, B-cyclohexylaminobutyraldehyde, ,B-nonylaminobutyraldehyde, p-(2-ethylhexyl)-aminobutyraldehyde, ,8- dodecylaminobutyraldehyde, fi-octaclecylaminobutyraldehyde, [3-di-methylaminobutyraldehyde, fl-diethylaminobutyraldehyde, ,B-dibutylaminobutyraldehyde, fi-methyl- S-cyclohexylaminobutyraldehyde, ,6 dinonylaminobutyraldehyde, 18-dimethylaminopivaldehyde, fl-diethylarninopivaldehyde, p-dibutylaminopivaldehyde, fl-dinonylaminopivaldehyde, B cyclohexylaminopivaldehyde, B nonylaminopivaldehyde, fi-dodecylaminopivaldehyde, fi-octadecylaminopivaldehyde, w, {3-, and 'y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylaminobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof produced by the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-p-toluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

3. In the manufacture of polyvinyl alcohol fibers of improved dyeability, the steps which comprise preparing an aqueous spinning fluid comprising a mixture of an aqueous spinning fluid comprising a mixture of an aque ous solution of polyvinyl alcohol and a water-insoluble acetalized polyvinyl alcohol in finely-divided form having a particle size of at most 30/.t, said acetalized polyvinyl alcohol being acetalized with at least one aldehyde containing basic nitrogen and at least one aldehyde free from basic nitrogen, said polyvinyl alcohol being acetalized with said last-named aldehyde and with said first-named aldehyde simultaneously, whereby said acetalized polyvinyl alcohol contains basic nitrogen, and spinning said fluid to form fibers therefrom, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methylarninoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethyla-minoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, fiaminopropionaldehyde, 8 methylaminopropionaldehyde, [3-ethylaminopropionaldehyde, fi-cyclohexylaminopropionaldehyde, ,8-dodecylaminopropionaldehyde, /3- aminobutyraldehyde, fi-methylaminobutyraldehyde, B- ethylaminobutyraldehyde, fi-butylaminobutyraldehyde, B- cyclohexylaminobutyraldehyde, ,8- nonylaminobutyraldehyde, 8-(2-ethylhexyl)-aminobutyraldehyde, fi-dodecylaminobutyraldehyde, ,B-octadecylaminobutyraldehyde, [3- di-methylaminobutyraldehyde, p diethylaminobutyraldehyde, B-dibutylaminobutyraldehyde, B-methyl-B-cyclohexylaminobutyraldehyde, fl-dinonylaminobutyraldehyde, fl-dimethylaminopivaldehyde, fl-diethylaminopivaldehyde, fl-dibutylaminopivaldehyde, B-dinonylaminopivaldehyde, fi cyclohexylaminopivaldehyde, B nonylaminopivaldehyde, fi-dodecylaminopivaldehyde, p-octadecylaminopivaldehyde, w, 5-, and y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylanimobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof produced by the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-ptoluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

4. In the manufacture of polyvinyl alcohol fibers of improved dyeability, the steps which comprise preparing an aqueous spinning fluid comprising a mixture of an aqueous solution of polyvinyl alcohol and a waterinsoluble acetalized polyvinyl alcohol in finely-divided form having a particle size of at most 30 said acetalized polyvinyl alcohol being acetalized with at least one aldehyde containing basic nitrogen and at least one aldehyde free from basic nitrogen, said polyvinyl alcohol being acetalized with said last-named aldehyde after being acetalized with said first-named aldehyde, whereby said acetalized polyvinyl alcohol contains basic nitrogen, and spinning said fluid to form fibers therefrom, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methylaminoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, flaminopropionaldehyde, [3 methylaminopropionaldehyde, 3 ethylaminopropionaldehyde, B cyclohexylaminopropionaldehyde, B-dodecylaminopropionaldehyde, p-aminobutyraldehyde, [3 methylaminobutyraldehyde, [3 ethylaminobutyraldehyde, ,6- butylaminobutyraldehyde, B- cyclohexylaminobutyraldehyde, B nonylaminobutyraldehyde, B-(Z-ethylhexyl)-aminobutyraldehyde, fi-dodecylaminobutyraldehyde, fl-octadecylaminobutyraldehyde, ,8- dimethylaminobutyraldehyde, 13 diethylaminobutyraldehyde, [3-dibutylaminobutyraldehyde, p-methyl-li-cyclohexylaminobutyraldehyde, B-dinonylaminobutyraldehyde, fi-di-methylaminopivaldehyde, fl-diethylaminopivaldehyde, fi-dibutylaminopivaldehyde, fl-dinonylaminopivaldehyde, p cyclohexylaminopivaldehyde, [3 nonylaminopivaldehyde, p-dodecylaminopivaldehyde, B-octadecylaminopivaldehyde, 11-, [3-, and 'y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylaminobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof produced by the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-p-toluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

5. In the manufacture of polyvinyl alcohol fibers of improved dyeability, the steps which comprise preparing an aqueous spinning fluid comprising a mixture of an aqueous solution of polyvinyl alcohol and a waterinsoluble acetalized polyvinyl alcohol in finely-divided form having a particle size of at most 30g, said acetalized polyvinyl alcohol being acetalized with at least one aldehyde containing basic nitrogen, whereby said acetalized polyvinyl alcohol contains basic nitrogen, and spinning said fluid to form fibers therefrom, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methylarninoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, ,3- aminopropionaldehyde, [3 methylaminopropionaldehyde, ,8 ethylaminopropionaldehyde, a cyclohexylaminopropionaldehyde, 8-dodecylaminopropionaldehyde, fl-aminobutyraldehyde, [3 methylaminobutyraldehyde, 18 ethylaminobutyraldehyde, B-butylaminobutyraldehyde, B-cyclohexylaminobutyraldehyde, [3 nonylaminobutyraldehyde, B-(2-ethylhexyl)-aminobutyraldehyde, 3 dodecylaminobutyraldehyde, ,8 octadecyla-minobutyraldehyde, 18. dimethylaminobutyraldehyde, fl-diethylaminobutyraldehyde, fi-dibutylaminobutyraldehyde, ,8 methyl B cyclohexylaminobutyraldehyde, ,B-dinonylaminobutyraldehyde, 13- dimethylaminopivaldehyde, B diethylaminopivaldehyde, p-dibutylaminopivaldehyde, fl-dinonylaminopivaldehyde, [3 cyclohexylaminopivaldehyde, 8 nonylaminopivaldehyde, 3-dodecylaminopivaldehyde, B-octadecylaminopivaldehyde, 01,-, and -pyridinealdehyde, p-aminobenzaldehyde, p-dimethylaminobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof produced by the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-p-toluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

6. A spinning fluid for the manufacture of polyvinyl alcohol fibers of improved dyeability, which comprise a mixture of an aqueous solution of polyvinyl alcohol and a water-insoluble acetalized polyvinyl alcohol in finely-divided form having a particle size of at least 30 said acetalized polyvinyl alcohol being acetalized with at most one aldehyde containing basic nitrogen and at least one aldehyde free from basic nitrogen, whereby said acetalized polyvinyl alcohol contains basic nitrogen, said aldehyde containing basic nitrogen being selected from the group consisting of aminoacetaldehyde, methyla-minoacetaldehyde, ethylaminoacetaldehyde, butylaminoacetaldehyde, cyclohexylaminoacetaldehyde, nonylaminoacetaldehyde, dodecylaminoacetaldehyde, octadecylaminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, dibutylaminoacetaldehyde, dinonylaminoacetaldehyde, fi-aminopropionaldehyde, ,B-methylaminopropionaldehyde, fl-ethylaminopropionaldehyde, ,8- cyclohexylaminopropionaldehyde, ,8 dodecylaminopropionaldehyde, p aminobutyraldehyde, [3 methylaminobutyraldehyde, fl-ethylaminobutyraldehyde, ,3-butylaminobutyraldehyde, fl-cyclohexylaminobutyraldehyde, B-nonylaminobutyraldehyde, B-(Z-ethylhexyl) arninobutyraldehyde, p-dodecylaminobutyraldehyde, ,B-octadecylaminobutyraldehyde, fi-dimethylaminobutyraldehyde, fl-diethylaminobutyraldehyde, 13-dibutylaminobutyraldehyde, B- methyl fi cyclohexylaminobutyraldehyde, B dinonylamino-butyraldehyde, B-dimethylaminopivaldehyde, fl-diethylaminopivaldehyde, fi-dibutylaminopivaldehyde, fidinonylaminopivaldehyde, [3 cyclohexylaminopivaldehyde, B-nonylaminopivaldehyde, p-dodecylaminopivaldehyde, 18-0ctadecylaminopivaldehyde, w, 13, and 'y-pyridinealdehyde, p-aminobenzaldehyde, p-dimethylaminobenzaldehyde, the acetals thereof, and the quaternary derivatives thereof produced by the action of alkylating agents selected from the group consisting of methyliodide, ethylbromide, dodecylbromide, benzylchloride, allyl chloride, dimethylsulfate, methyl-p-toluenesulfonate, ethyleneoxide, and the acetals of said quaternary derivatives.

References Cited by the Examiner UNITED STATES PATENTS 2,890,927 7/59 Suyama 1=854 2,895,786 7/59 Schlack 18-54 2,909,502 10/59 Matsumoto et al. 260-874 2,992,204 7/ 61 Osugi et a1. 260-874 MURRAY TILLMAN, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Nov 3,211,685 October 12, 1965 Osamu Fukushima et al I It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 67, for "entrely" read entirely M column 3, line 55, for exampes" read examples column 9, line 21, for "least" read most line 23, for "most" read least I Signed and sealed this 21st day of June 1966 (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. IN THE MANUFACTURE OF POLYVINYL ALCOHOL FIBERS OF IMPROVED DYEABILITY, THE STEPS WHICH COMPRISE PREPARING AN AQUEOUS SPINNING FLUID COMPRISING A MIXTURE OF AN AQUEOUS SOLUTION OF POLYVINYL ALCOHOL AND A WATERINSOLUBLE ACETALIZED POLYVINYL ALCOHOL AND A WATERINSOLUBLE ACETALIZED POLYVINYL ALCOHOL IN FINELY-DIVIDED FORM HAVING A PARTICLE SIZE OF AT MOST 30U, SAID ACETALIZED POLYVINYL ALCOHOL BEING ACETALIZED WITH AT LEAST ONE ALDEHYDE CONTAINING BASIC NITROGEN AND AT LEAST ONE ALDEHYDE FREE FROM BASIC NITROGEN, WHEREBY SAID ACETALIZED POLYVINYL ALCOHOL CONTAINS BASIC NITROGEN AND SPINNING SAID FLUID TO FORM FIBERS THEREFROM, SAID ALDEHYDE CONTAINING BASIC NITROGEN BEING SELECTED FROM THE GROUP CONSISTING OF AMINOACETALDEHYDE, METHYLAMINOACETALDEHYDE, ETHYLAMINOACETALDEHYDE, BUTLAMINOACETALADEHYDE, CYCLOHEXYLAMINOACETALDEHYDE, NONYLAMINOACETALDEHYDE, DODECYLAMINOACETALDEHYDE, OCTADECYLAMINOACETALDEHYDE, DIMETHYLAMINOACETALDEHYDE, DIETHYLAMINOACETALDEHYDE, DIBUTYLAMINOACETALDEHYDE, DIMONYLAMINOACETALDEHYDE, B/AMINOPROPIONALDEHYDE, B-METHYLAMINOPROPIONALDEHYDE, B-ETHYLAMINOPROPIONALDEHYDE, B-CYCLOHEXYLAMINOPROPIONALDEHYDE, B-DODECYLAMINOPROPIONALDEHYDE, B-AMINOBUTYRALDEHYDE, B-METHYLAMINOBUTYRALDEHYDE, B-THYLAMINOBUTYRALDEHYDE, B-BUTYLAMINOBUTYRALDEHYDE, B-CYCLOHEXYLAMINOBUTYRALDEHYDE, B-NONYLAMINOBUTYRALDEHYDE, B-(2ETHYLHEXYL)-AMINOBUTYRALDEHYDE, B-DODECYLAMINOBUTYRALDEHYDE, B-OCTADECYLAMINOBUTYRALDEHYDE, B-DIMETHYLAMINOBUTYRALDEHYDE, B-DIETHYLAMINOBUTYRALDEHYDE, B-DIBUTYLAMINOBUTYRALDEHYDE, B-METHYL-B-CYCLOHEXYLAMINOBUTYRALDEHYDE, B-DIMONYLAMINOBUTYRALDEHYDE, B-DIMETHYLAMINOPIVALDEHYDE, B-DIETHYLAMINOPIVALDEHYDE, B-DIBUTYLAMINOPIVALDEHYDE, B-DIMONYLAMINOPIVALDEHYDE, B-CYCLOHEXYLAMINOPIVALDEHYDE, B-NONYLAMINOPIVALDEHYDE, B-DODECYLAMINOPIVALDEHYDE, B-OCTADECYLAMINOPIVALDEHYDE, A-, B-, AND Y-PYRIDINEALDEHYDE, P-AMINOBENZALDEHYDE, P-DIMETHYLAMINOBENZALDEHYDE, THE ACETALS THEREOF, AND THE QUATERNARY DERIVATIVES THEREOF PRODUCED BY THE ACTION OF ALKYLATING AGENTS SELECTED FROM THE GROUP CONSISTING OF METHYLIODIDE, ETHYLBROMIDE, DODECYLBROMIDE, BENZYLCHLORIDE, ALLYL CHLORIDE, DIMETHYLSUFATE, METHYL-P-TOLUENESULFONATE, ETHYLENEOXIDE, AND THE ACETALS OF SAID QUATERNARY DERIVATIVES. 